Basic dyes



United States Patent Ofiiice 3374i Patented ,Mar. 19, 1968 .3 374 221 Inthe followingexamples the parts and percentages are X by weight and thetemperatures in degrees centigrade. RQIandwEntscheI and Curt MuellerBasel ,and Walter Wehrli, Riehen, Switzerland, assigilors to Sandoz Ltd.EXAMPLE 1 (also n w as a dQZ A-G-), Basel, Switzerland 18.4 parts ofN-ethyl-N-fi-chloroethyl-aminobenzene N goriginal PP 1964: are dissolvedin 100 parts of methanol and after adding $43 37. fi ifl app a vJune1966! 6.3 parts of 1,1-dimethyl-hydrazine the solution is heated Q atthe boil with reflux for 24 hours. The solvent is C] t' S l d ,21 1961 i1 -3- 6 2. 22298762 men evaporated and the pulverized res1due washedwith 21 4398/62 10 little benzene and .dried. It is dissolved in 400parts of zclaimslycl. 260 20 5) .water and coupled with a hydrochloricacid diazonium solution produced in the normal way from 16 parts of l-The P es PPI CQH a dw s n f a p amino-2-chloro-4-nitrobenzene. The dyeis precipitated rial l ry 13, 1954 which PP with a little sodiumchloride, filtered, washed with 1% i is a C0I1tiI1llatl0n-in"Part Of O-p g PP 15 sodium chloride solution and dried. A dark red-brown tionsSer. 1 ,.fi p 19, ,6 now Pawnt powder with a melting point of 220-221 isobtained. The 2, Sen filed 0n P 1952i dye is purified byrecrystallization and its melting point i now Patent No. 3,252,965; Ser.No. 250,787, filed on h 23443 Jan. 11, 1963 (now abandonedhser. ;No250,788, filed Dyeing Example A on Jan. 11, 1963 (now abandoned); Ser.No. 250,789, 20 filed on Jan. 11', 1963 (now abandoned); Ser. No. 300,20 parts of the dye obtained according to Example 1 .068, =filed.on Aug.5, 1963 (now abandoned), and relates are intimately mixed with :80 partsof dextrin in a ball .to basicdyestuifsand their production. mill ,for48 hours.

More specifically the invention relates to the novel 1 part of thispreparation is pasted with 1 part .of acetic basic dyestufls of theformulae acid 400 .partsof distilled water at 60 are poured NHE a;

OzHs and - (orient-02s N= mim INH II The Anion" may be organic orinorganic, for example over the :paste with constant agitation and thewhole the ion of methyl sulfate, sulfate, disulfate, perchlorate, boiledfor a short time. The solution is diluted with 7600 chloride, bromide,iodide, phosphorus molybdate, phosparts of distilled water, and 2 partsof glacial acetic acid phorus tungsten inolybdate, 'benzenesul fonate,4-chloroare added. 100 parts of Orlon (registered trademark)benzenesulfonate,maleinate or oxalate. are entered in this bath at 60.The material was pre- The new dyes are excellent for dyeing, padding andtreated for 10-15 minutes at 60 in a bath of 8000 parts printingmaterials of polymers containing more than 80% of water and 2 parts ofglacial acetic acid. The dyebath is acrylonitrile e.g.polyacrylonitr-ile, e.g. Orlon (registered brought to 100 in 30 minutes,boiled for 1 hour and the trademark), and copolymers containing 80-90%acrylo- 5O material rinsed. A level red dyeing of excellent lightfastnitrile and 20-10% vinyl acetate, methyl acrylate or ness and verygood wet fastness is obtained. methyl methacrylate.

These products are marketed under the following Pad dyeing Example 3names, most of which are registered trademarks: Acri-lan (the copolymerof 185% acrylonitrile and 15% vinyl 2196- A padding liquor is preparedwith:

t ate or vinyl pyridine), Orlon, Dralon, .Courtelle, .Qrylor, PartsDynel, etc. per liter The dyeings on these materials obtained with the.afore- Dye (corresponding to the dyeing preparation prosaid new .dyespossess good tastness to light, washing, duced in the previous dyeingexample) 5O perspiration, sublimation, pleating, decatizing, pressing,Sodium ,alginate 3 water, sea water, bleaching, drycleaning, crossdyeing, Acetic acid conc. S

and solvents. Cationic softener e.g. .a condensation product of 1 molThe new dyes have very good solubility in water. They stearic acid .and1 mol triethanolamine 20 r dyed to best .advantage'from aqueous mediumwhic Glaubers salt 25 is neutral or acid and of boiling temperature.

The commercially available retarding agents .can be Polyacrylonitrilefiber material is padded cold by the used in dyeing .without adverseeffect, although the new usual method on a 2 or 3 bowl pad. The pick-upis dyes produced perfectly level dyeings on the above-named Afterintermediate drying for a short time at on polymers and copolymersWithout the addition of these tenters, in a hot flue or by infraredradiation, the material agents. The dyes can be applied in closedequipment and 70 is fixed for 1-3 minuteswith dry air at l70-l90 onunder pressure, as they are highly stable in Water to protenters,subsequently rinsed, soaped and rinsed again. A

longed boiling. red dyeing with excellent light fastness is obtained.

Textile printing example A printing paste is made up with:

Parts Dye (corresponding to the dyeing preparation produced in theprevious dyeing example) 75 Acetic acid cone. Sodium alginate thickening450 Cationic softener, eg a Condensation product of 1 mol stearic acidand 1 mol triethanolamine 25 Glaubers salt 25 Water 415Polyacrylonitrile fi'ber material is printed according to the usualhand-block printing process and subsequently air-dried, steamed for20-30 minutes in a star steamer with saturated steam, rinsed, soaped,rinsed again and dried. On polyacrylonitrile fabrics a red print withvery good fastness properties is obtained.

EXAMPLE 2 37.5 parts of the dye 2-chloro-4-nitro-4-(N-ethyl-N-dimethyl-aminoethyl) amino 1,1 azobenzene are dissolved at roomtemperature in 900 parts of chlorobenzene. 7.1 parts of freshly preparedgaseous chloramine are added to this solution at 30 with thoroughstirring in the course of 3 hours. The dye salt formed is precipitatedand can be isolated by filtration from the chlorobenzene.

On drying, a red powder is obtained which dyes Orlon (registeredtrademark) in level red shades of good light and wet fastness. In eachcase the production of chloramine is effected by the usual methodsdescribed in the literature (cf. e.g. G. H. Coleman, InorganicSyntheses, vol. I, p. 59; Omietanski, Inorganic Syntheses, vol. V, p.92; Gmelin, Handbook of Inorganic Chemistry, 8th edition (1926), p.418).

An ethereal chloramine solution, produced for example according toInorganic Syntheses I, can be used in place of gaseous chloramine.

In the latter case the dye salt is produced by dissolving 37.5 parts ofthe dye2-chloro-4-nitro-4'(N-ethyl-N-dimethyl-aminoethyl)-amino-1,1'-azohenzeneat room temperature in 1500 parts of chlorobenzene. In the course of 1hour the ether solution containing about 7 parts of chloramine is runinto this solution with thorough stirring at 25-30 C. The dye salt isprecipitated and can be filtered otf.

EXAMPLE 3 17.25 parts of l-amino 2 chloro 4 nitrobenzene in finelydivided form are stirred into 100 parts of hydrochloric acid at 0". Onthe addition of 27 parts of a 4nsodium nitrate solution the diazoniumsalt solution is formed in almost quantitative yield within 30 minutesat 0.

By adding 21 parts of a compound of the formula CaHs in solution in 100parts of glacial acetic acid at 0", the desired dye formation commencesimmediately. The coupline reaction is accelerated by rendering thesolution weakly acid with sodium acetate. On completion of coupling thedye is filtered off, rinsed free of salt with water and dried.

The dye obtained is of low water solubility, and has the formula /CtHr-N 4- It can be used directly for dyeing polyacrylonitrile byapplying it in an acid, preferably mineral acid dyebath.

The resulting dyeings are level and have good fastness properties.

The azo compound used for the production of the dye described can beobtained by the known method, i.e. by reacting N-fi-chloroethyl-N-ethylmetatoluidine with an excess ofmonomethylhydrazine at about 100", then separating the reaction productand distilling with high vacuum.

EXAMPLE 4 42.05 parts of the dye described in Example 3 are dissolved in1000 parts of chlorobenzene at 19 parts of dimethyls-ulfate in solutionin 19 parts of chlorobenzene are added dropwise with stirring, andstirring continued for 2 hours at 80-90". The solution is allowed tocool, the salt filtered off and dried. The dye salt is obtained as adark red powder. The compound of the formula dyes polyacrylonitrile indark red shades.

EXAMPLE 5 onsosot NH1 93 C H:

l C2 4-N a): e CHaOSOs -N Cr r with 19 parts of dimethyl sulfate andsubsequently combined with a hydrochloric acid solution of diazoniumsalt prepared with 17.25 parts of 1-amino-2-chloro-4- nitrobenzene, andthe dye salt isolated by the known methods.

The pure chloride can be produced with the aid of an anion exchanger.The dye of the formula Cm. melts at 218-219".

EXAMPLE 6 8 parts of finely pulverized, anhydrous sodium nitrite areadded to 105 parts of sulfuric acid 96% at the temperature range ofoil-70. When this is completely dissolved, the nitrosyl'sulfuric acidformed is cooled to 1520. 100 parts of glacial acetic acid are run in at20 and then 16.3 parts of Z-amino-S-nitrobenzonitrile are strewn in,followed by a further 100 parts of glacial acetic acid.

The solution is stirred for 2-3 hours at 15. The excess nitrite isdestroyed by the addition of 5 parts of urea and the solution thendischarged into 350 parts of water. The diazonium salt solution at 0 isfiltered and reacted with 24.2 parts of a compound of the formula NH: EB

in solution in 200 parts of water,

The coupling reaction slowly commences; the pH value is brought to 5.5by the addition of ammonia, upon which the coupling reaction takes placeimmediately so that the product can be filtered, rinsed and dried atonce. The dye salt of the formula IIIH: 69 C H4N(CH) CzHs NHg

is obtained which has a melting point of 229-230 and gives ruby shades.

EXAMPLE 7 18.4 parts of N-ethyl-N-fi-chloroethyl-aminobenzene aredissolved in 100 parts of ethanol. 9.1 parts of N- aminopyrrolidine areadded and the solution boiled for 24 hours with reflux. The solvent isthen volatilized and the pulverized residue washed with a littlebenzene. The dried product is dissolved in 400 parts of water and cou'pled with a hydrochloric acid diazonium salt solution, prepared in thenormal manner from 16 parts of l-amino-2- ch1oro-4-nitrobenzene. Oncompletion of coupling some sodium chloride may be added if necessary toprecipitate the dye, which is then filtered 01f, washed with 1% sodiumchloride solution, and dried. It is obtained as a dark brown-red powder.The coupling component named above can be prepared in the form of anaqueous solution of about 53% strength: 18.4 parts ofN-ethyl-N-B-chloroethyl-aminobenzene are stirred into 20 parts of water,9.1 parts of N-aminopyrrolidine are added and the mixture heated at 90with vigorous stirring. After about 2 hours a clear solution is formed.1.4 parts of dimethyl sulfate are added to bind the excessN-aminopyrrolidine. The

solution is then cooled and the preparation employed for the azocoupling reaction.

6 EXAMPLE 8 19.8 parts ofN-ethyl-N-fl-chloroethyl-3-methyl-1-arninobenzene are dissolved in 100parts of ethanol. 10.6 parts of N-aminopiperidine are added and thesolution boiled for 24 hours with reflux. The solvent is thenvolatilized and the pulverized residue Washed with a little benzene. Thedried product is dissolved in 400 parts of water and coupled with ahydrochlorid acid diazonium salt solution, prepared in the normal mannerfrom 16 parts of 1- amino-2-chloro-4-nitrobenzene. On completion ofcoupling some sodium chloride may be added if necessary to precipitatethe dye, which is then filtered off, washed with 1% sodium chloridesolution, and dried. It is obtained as a dark brown-red powder.

The coupling component named above can be prepared in the form of anaqueous solution of about 53% strength: 19.8 parts ofN-ethyl-N-fl-chloroethyl-3-methyl-l-aminobenzene are stirred into 20parts of water, 10.6 parts of N-aminopiperidine are added and themixture heated at 90 with vigorous stirring. After about 2 hours a clearsolution is formed. 1.4 parts of dimethyl sulfate are added to bind theexcess N-aminopiperidine. The solution is then cooled and thepreparation employed for the azo coupling reaction.

EXAMPLE 9 18.4 parts of N-ethyl-N-B-chloroethyl-l-amino-benzeneamino-morpholine are added and the solution boiled for 24 hours withreflux. The solvent is then volatilized and the pulverized residuewashed with a little benzene. The dried product is dissolved in 400parts of water and coupled with a hydrochloric acid diazonium saltsolution prepared in the normal manner from 20 parts of l-amino-2-bromo-4-nitro-benzene. On completion of coupling some sodium chloridemay be added if necessary to precipitate the dye, which is then filteredoff, washed with 1% sodium chloride solution, and dried. It is obtainedas a dark brown-red powder.

The coupling component named above can be prepared in the form of anaqueous solution of about 53% strength: 18.4 parts ofN-ethyl-N-fi-chloroethyl-l-amino-benzene are stirred into 20 parts ofwater, 10.8 parts of N-aminomorpholine are added and the mixture heatedat 90 with vigorous stirring. After about 2 hours a clear solution isformed. 1.4 parts of dimethyl sulfate are added to bind the excessN-aminomorpholine. The solution is then cooled and the preparationemployed for the azo coupling reaction.

The aforesaid further valuable basic monoazo dyes I and H can beproduced by the process given in the above examples. Dyestuff I producesyellow shades and dyestufi II produces orange shades when used fordyeing polyacrylonitrile.

Having thus disclosed the invention, what is claimed is:

1. The basic dyestuff of the formula:

NH: a)

Anion 2. The basic dyestuff of the formula:

Anion No references cited.

CHARLES B. PARKER, Primary Examiner.

D. PAPUGA, Assistant Examiner.

1. THE BASIC DYESTUFF OF THE FORMULA: